Process for the production of synthesis gas

ABSTRACT

Process and system for the production of synthesis gas from a hydrocarbon feed stock comprising the steps of endothermic and/or adiabatic catalytic steam reforming and autothermal steam reforming in series, wherein the steam reforming is carried out in one or more endothermic stages in series or in one or more adiabatic steam reforming stages in series with intermediate heating of feed stock gas leaving the adiabatic reforming stages and wherein carbon monoxide containing gas characterised by having a molar ratio of hydrogen to carbon of less than 4.5 is added prior to at least one of the endothermic or adiabatic steam reforming stages and/or prior to the autothermal steam reforming step.

This is a divisional of U.S. application Ser. No. 10/667,389, filed Sep.23, 2003, now U.S. Pat. No. 7,241,401 which claims priority of DenmarkPatent Application PA 2002 01435, filed Sep. 26, 2003, the entiredisclosures of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention concerns the production of synthesis gas by a sequence ofone or more endothermic and/or adiabatic steam reforming and autothermalsteam reforming.

2. Description of the Related Art

U.S. Pat. No. 6,375,916 discloses a method for preparing synthesis gasby installing a pre-reformer upstream an autothermal reformer (ATR). Thepre-reformer is used to remove or reduce the contents of higherhydrocarbons from a hydrocarbon feed stream with the advantage thatlower steam to carbon ratios can be employed without soot formation inthe ATR. However, the process described is not able to produce asynthesis gas with an hydrogen to carbon monoxide ratio close to 2.0unless either the steam-to-carbon ratio is very low (probably less than0.2) or the difference between the exit temperature from and the inlettemperature to the ATR is very high. In the former case this may givedifficulties with operating the prereformer without carbon formation andin the latter case the amount of oxygen used may be disadvantageouslyhigh.

U.S. Patent Application Publication No. 2001/0051662 by Arcuri et al.discloses a method to produce synthesis gas involving among others themixing of tail gas and a hydrocarbon feedstock and feeding the resultantmixture to an adiabatic pre-reformer. The effluent from the adiabaticpre-reformer is passed to a synthesis gas generator for production ofsynthesis gas.

If the synthesis gas generator is an autothermal reformer, a synthesisgas with a hydrogen to carbon monoxide ratio of about 2.0 can beproduced. However, recirculation of the tail gas to the feed to theadiabatic pre-reformer is disadvantageous because the risk of carbonformation will be higher in the prereformer. This means that the processmust be operated at a higher steam-to-carbon ratio. Low steam-to-carbonratios are generally preferable in Fischer-Tropsch to improve economics.

U.S. Pat. No. 6,525,104 describes a process in which a heat exchangereformer is placed in series with and upstream of an AutothermalReformer for production of synthesis gas. Recirculated carbon dioxide isadded to the feed stream to the heat exchange reformer. The amount ofrecirculated carbon dioxide is adjusted to between 20 and 60% of thecarbon from hydrocarbons in the feed stream to the plant. No prereformeris used. The carbon dioxide is recovered and recirculated from one ofseveral possible locations downstream the Autothermal Reformer.

This concept has several disadvantages for production of synthesis gasfor Fischer-Tropsch processes. One disadvatage is that a costly step ofseparating carbon dioxide from a mixed gas stream is needed. Anotherdisadvantage is that it may not be possible with the amount ofrecirculated carbon dioxide to produce a synthesis gas with the desiredhydrogen-to-carbon monoxide ratio (i.e. a H₂/CO ratio of approximately2.00) except possibly at relatively high steam-to-carbon ratios. In theexamples given in U.S. Pat. No. 6,525,104 a steam-to-carbon ratio of 1.5is used. A steam-to-carbon ratio of 1.5 will in many cases render aprocess for production of Fischer-Tropsch products uneconomical.

In another embodiment disclosed in U.S. Pat. No. 6,525,104 a higherhydrocarbon (hydrocarbons with two or more carbon atoms) and carbondioxide containing gas stream is recirculated to the feed to anadiabatic prereformer placed upstream and in series with the heatexchange reformer and the autothermal reformer. If this recirculated gasstream is a tail gas from a Fischer Tropsch synthesis section, then thisprocess would have the disadvantage of an increased risk of carbonformation in the prereformer as described above. Hence, a highersteam-to-carbon ratio would be needed. This may appear surprising as itis generally accepted that passing higher hydrocarbon containing gasstreams through an adiabatic prereformer is advantageous from a processeconomic point of view.

SUMMARY OF THE INVENTION

The invention is a process for the production of synthesis gas from ahydrocarbon feed stock comprising the steps of endothermic and/oradiabatic catalytic steam reforming and autothermal steam reforming inseries, wherein the steam reforming is carried out in one or moreendothermic stages in series and/or in one or more adiabatic steamreforming stages in series with intermediate heating of feed stock gasleaving the adiabatic reforming stages and wherein carbon monoxidecontaining gas characterised by having a molar ratio of hydrogen tocarbon of less than 4.5 is added after at least one of the endothermicor adiabatic steam reforming stages and/or prior to the autothermalsteam reforming step.

The invention also concerns a steam reforming system for use in theabove synthesis gas production process.

A plant for production of synthetic diesel and other synthetichydrocarbons consists of three main units. In the first main unitsynthesis gas (a mixture of hydrogen and carbon oxides) is produced fromthe feedstock which is usually natural gas or a similar lighthydrocarbon feedstock. In the second main unit, the actual hydrocarbonsynthesis takes place usually by the Fischer-Tropsch synthesis. In thefinal unit often known as the Product Work-up unit the raw products arerefined and/or separated to give the desired end products. The presentinvention relates to an improved method for production of synthesis gas.

Today one of the most cost effective and efficient methods forproduction of synthesis gas is by Autothermal Reforming (ATR). In ATRthe light hydrocarbon feedstock with addition of steam reacts with asub-stoichiometric amount of oxygen to produce synthesis gas. An ATRreactor consists of a burner, a combustion chamber, and a catalyst bedin a refractory lined pressure shell. The ATR reactor is a conventionalprocess unit as described in the art.

For the Fischer-Tropsch synthesis to be as effective as possible, aspecific synthesis gas composition is often desired. In many cases thedesired synthesis gas composition is given by the ratio of the hydrogencontent to the carbon monoxide content. The desired ratio is oftenapproximately 2.0. With most operating conditions ATR is not able toproduce this ratio from natural gas, which generally has a high atomicH/C ratio often close to 4. In order to obtain the desired H₂/CO ratioin the product gas, additional feedstock with a low atomic H/C ratiomust be added to a location upstream the ATR reactor. This additionalfeedstock could be carbon dioxide (requiring that pure carbon dioxide isrecovered from an impure gas stream) or a tail gas, which is essentiallya byproduct from the Fischer-Tropsch synthesis unit and/or the ProductWork-up unit. The main components in the tail gas are usually carbonmonoxide, carbon dioxide, hydrogen, various light paraffinic andolefinic hydrocarbons and sometimes inert gases such as nitrogen andargon.

As described above, it is hardly possible to produce a synthesis gaswith a composition of H₂/CO of approximately 2 without recycle. This canbe understood from the following simplified explanation.

The desired product has a ratio of atomic hydrogen to atomic carbon(H/C)_(product) of approximately 4. The feed consisting of natural gas(or other light hydrocarbon component) and steam has a (H/C)_(feed)ratio of typically 4.5-7.5 depending on the steam-to-carbon ratio andthe hydrocarbon stream composition. As an example a mixture of 100 molesmethane and 60 moles steam corresponding to a steam-to-carbon ratio of0.60 will have an atomic (H/C) ratio of 5.20.

The (H/C)_(product) is lower than (H/C) feed and hence addition of a(recycle) stream with an atomic (H/C) ratio less than (H/C)_(product) isneeded. The desired H₂/CO ratio in the product gas may often be between1.7 and 2.3 corresponding to (H/C)_(product) equal to 3.4-4.6.

It is recognized that the above is a simplified representation (e.g.since some of the carbon in the feed will remain in methane or beconverted into carbon dioxide).

However, for practical applications this explanation is suitable and theratio of atomic hydrogen to atomic carbon in the recycle gas must beequal to or below 4.5 ((H/C)_(recycle)<=4.5)

Synthesis gas production may account for more than 50% of the totalcapital cost in a Fischer-Tropsch plant. For a plant based on ATR alarge fraction of the cost of the synthesis gas production unit (e.g.40-60%, depending upon the scale and specific site and technology)arises from the air separation unit needed to produce oxygen. Hence,there is a considerable interest in methods for reducing the oxygenconsumption per unit of synthesis gas produced.

Increasing the temperature of the hydrocarbon feedstock before it entersthe ATR reactor and/or reducing the steam-to-carbon (S/C) ratio reducesthe oxygen consumption. The S/C-ratio is defined as the ratio of theamount of steam to carbon from hydrocarbons in the hydrocarbonfeedstock. Both of the described methods have disadvantages. Increasingthe feedstock temperature increases the risk of cracking of thehydrocarbons in the feedstock and means that more expensive materialsmust be used in the heaters or heat exchangers upstream the ATR.Reducing the S/C-ratio decreases the margin to soot formation in the ATRand may also increase the risk of cracking of hydrocarbons in heaters orheat exchangers upstream the ATR. The present invention concerns aprocess, whereby both of these disadvantages are avoided while theoxygen consumption is reduced considerably.

According to the present invention a reformer unit is placed before andin series with the ATR reactor. The reformer unit receives heat from ahot process gas stream and steam reforming of hydrocarbons takes placein the reformer unit as illustrated below for methane:CH₄+H₂O

3H₂+CO  (1)The steam reforming reaction is accompanied by the Shift Reaction:CO+H₂O

H₂+CO₂  (2)

The above two reactions are in most cases close to equilibrium at thereformer unit outlet. If higher hydrocarbons (hydrocarbons with 2 ormore hydrocarbon atoms) are present in the reformer unit feed stream,these are also steam reformed according to reactions similar to theabove.

It is described in the art (e.g. U.S. Pat. No. 6,375,916) that apre-reformer can be placed upstream the ATR in a Fischer-Tropsch plant.In this case, the reformer unit is placed between the pre-reformer andthe ATR, i.e. in series and downstream the pre-reformer and in seriesand upstream the ATR.

In the process of the invention, the carbon monoxide containing gas isexemplified by use of a tail gas. Tail gas is added to the reformer uniteffluent and/or to the feed stream to the reformer unit (after theprereformer if such is present). Tail gas may also be added betweenindividual stages of the reformer unit as described below. Addition of areformer unit upstream the ATR provides a means for adding heat into theATR feed stream, while maintaining a reasonable temperature at the ATRreactor inlet. At the same time a sufficient margin to the soot pointsfor the ATR are maintained and the risk of cracking from hydrocarbons inthe ATR feed stream is reduced. Furthermore, by addition of at leastpart of the tail gas to the reformer unit effluent, the risk of carbonformation in the prereformer and the reformer unit can be controlledallowing operation at a low steam-to-carbon ratio. Furthermore, theoxygen consumption per unit of produced synthesis gas is decreasedcompared to prior art without substantially affecting the synthesis gascomposition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the overall process scheme with the reformer unit.

FIG. 2 shows a specific embodiment of the process.

DETAILED DESCRIPTION OF THE INVENTION

A description of the process scheme with the reformer unit is given inFIG. 1. Desulphurised natural gas (1) or a similar feedstock is mixedwith steam (2) and preheated in the heat exchanger or heater (3) to thedesired inlet temperature to the adiabatic pre-reformer (4). Thistemperature is typically between 320-550° C. In the pre-reformer (4) thefollowing reactions take place:CO+H₂O

H₂+CO₂  (2)C_(n)H_(m) +nH₂O

nCO+½(m+2n)H₂  (3)3H₂+CO

CH₄+H₂O  (4)

At most conditions higher hydrocarbons (hydrocarbons with more than 1carbon atom) are completely removed. The last two reactions (4) and (2)are close to equilibrium at the exit temperature of the adiabaticpre-reformer (4). Typically, the catalyst in the adiabatic pre-reformeris nickel on a ceramic carrier.

Depending on the actual design of the desulphurisation unit, a smallleakage of sulphur to the prereformer may occur. With most prereformercatalysts this minute amount of sulphur will be adsorbed.

Tail gas (5) heated in heater or heat exchanger (12) may optionally beadded through line (6) to the pre-reformer effluent (21) to form thereformer unit feed stream (20). In the reformer unit (8) the reformerunit feed stream (20) is steam reformed according to the followingreactions:CH₄+H₂O

3H₂+CO  (1)CO+H₂O

H₂+CO₂  (2)C_(n)H_(m) +nH₂O

nCO½(m+2n)H₂  (3)

At most conditions the reformer unit effluent (22) will be virtuallyfree of higher hydrocarbons and reactions (1) and (2) above will beclose to thermodynamic equilibrium. Most preferably, the reformer uniteffluent (22) will have a temperature between 500° C. and 750° C. Theheat for the endothermic steam reforming reactions and for the heatingis supplied by heat exchange with a hot process gas stream (not shown inFIG. 1).

Heated tail gas is added to the reformer unit effluent through line (7)resulting in an ATR feed stream (23). The ATR feed stream (23) andoxidant (10) usually containing more than 90% oxygen is passed to theautothermal reformer (9) in which synthesis gas is produced andwithdrawn as product (11), which is sent to the Fischer-Tropschsynthesis section. The produced synthesis gas withdrawn from theautothermal reformer may (before being sent to the Fischer-Tropschsection) be used as heat source in a heat exchange reformer. The totalamount of tail gas added through line (6)(optional) and (7) is adjustedto give the desired exit gas composition from the autothermal reformer(9).

Steam reforming involves the risk of detrimental carbon formation on thecatalyst. Carbon may deposit on the catalyst either from methane, carbonmonoxide, higher paraffinic hydrocarbons or other components such asolefins.

For methane the carbon forming reaction may be expressed by:CH₄

C+2H₂  (5)

The risk of carbon formation from methane may often be evaluated bythermodynamics. This is often done as follows:

The composition assuming chemical equilibrium of the steam reforming andshift reactions (1-3) is calculated based on the feed stream compositionand the temperature and pressure. This should in principle be done ateach position in the reactor. However, experience shows that the risk ofcarbon formation from methane according to reaction (5) increases withtemperature. Based on the calculated equilibrium composition, thereaction quotient for reaction (5) is calculated. The reaction quotientQ_(c) is the ratio of the square of the partial pressure of hydrogen tothe partial pressure of methane (P² _(H2)/P_(CH4)). If the ratio ishigher than the equilibrium constant for reaction (5) at the sametemperature, carbon is not predicted to form. A similar approach forcarbon formation from carbon monoxide on a catalyst may be used byaddressing the reaction:2CO

C+CO₂  (6)

The formation of carbon on a catalyst from higher hydrocarbons in theform of paraffins can be expressed by:C_(n)H_(m)

nC+½mH₂ (n=2, 3, 4, . . . and m=2+2n)  (7)

At a given temperature it is stated in the art that the risk of carbonformation on the catalyst is reduced by increasing the ratio of steam tohigher hydrocarbons in the feed gas.

Finally, carbon formation on a reforming catalyst may occur from olefinsor other unsaturated hydrocarbons. It is generally important to minimisethe amount of unsaturated compounds in a gas in contact with a reformercatalyst as the rate of carbon formation may be very high as known inthe art.

The catalyst in the reformer unit may be either nickel-based catalystsand/or catalysts based on noble metals. With noble metals it is possibleto operate with lower steam-to-carbon ratios without detrimental carbonformation on the catalyst as described in the art, e.g. Rostrup-Nielsenet al., J. of Catalysis 144, pages 38-49, 1993, incorporated herein byreference. Often, the required amount of steam to avoid carbon formationincreases with increasing temperature. Hence, in one embodiment of thepresent invention nickel can be used at the zones in the reformer unitoperating at lower temperature, while noble metals can be used in thezones operating at higher temperatures.

The hydrogen content in the gas leaving the reforming unit is higherthan the content in the reformer unit feed gas. If tail gas is addedpartially or completely downstream the reformer unit, then the ratio ofhydrogen to higher hydrocarbons in the ATR feed stream is higher thanwhen the reformer unit is not present. Higher hydrocarbons may reactthermally crack) into carbonaceous species such as aromatics,polyaromatics and carbon at elevated temperatures. This can berepresented by the following reaction:C_(n)H_(m)

nC+½mH₂  (7)

Since a large amount of hydrogen is present in the process of theinvention, the risk of thermal cracking is reduced and/or the tail gasmay be preheated to a higher temperature increasing the syngasproduction per unit of oxygen consumed.

The removal of (part of) the higher hydrocarbons in the tail gas byreaction in the reformer unit is by itself beneficial in terms ofincreasing the margin to soot formation in the ATR.

The optimal design of the reformer unit and the distribution of tail gasdepends on a number of factors including natural gas composition,temperature, pressure and tail gas composition.

The catalytic activity for steam reforming in the reformer unit can beobtained either by conventional fixed beds of (pellet) catalysts, bycatalysed hardware, or by structured catalysts. In case of catalysedhardware, catalytic material is added directly to a metal surface. Thecatalytic coating of a metal surface (wash coating) is a well knownprocess (a description is given in e.g. Cybulski, A., and Moulijn, J.A., Structured catalysts and reactors, Marcel Dekker, Inc, New York,1998, Chapter 3, and references herein).

The appropriate material, preferable a ferritic steel containing Crand/or Al, is heated to a temperature preferably above 800° C. in orderto form a layer of Cr and/or Al oxide. This layer facilitates a goodadhesion of the ceramic to the steel. A thin layer of a slurrycontaining the ceramic precursor is applied on the surface by means ofe.g. spraying, painting or dipping. After applying the coat the slurryis dried and calcined at a temperature usually in the region 350-1000 C.Finally, the ceramic layer is impregnated with the catalytic activematerial.

Alternatively the catalytic active material is applied simultaneouslywith the ceramic precursor.

Catalysed hardware can in the present invention either be catalystattached directly to a channel wall in which the process gas flows orcatalyst attached to a metallic structured element forming a structuredcatalyst. The structured element serves to provide support to thecatalyst.

Further catalyst hardware is in form of catalyst being deposited inmetallic or ceramic structure, which is adhered to wall of the reactor.

Structured elements are devices comprising a plurality of layers withflow channels present between the adjoining layers. The layers areshaped in such a way that placing the adjoining layers together resultsin an element in which the flow channels can, for instance, cross eachother or can form straight channels. Structured elements are furtherdescribed in for instance U.S. Pat. Nos. 5,536,699, 4,985,230, EP patentapplication Nos. 396,650, 433,223 and 208,929, all of which areincorporated herein by reference.

Two types of structured elements are particularly suitable for theinventive process—the straight-channelled elements and thecross-corrugated elements.

The straight-channelled elements require adiabatic conditions andvarious geometries of these elements are possible. For example, straightchannel monoliths are suitable for use in the process of the inventionin the adiabatic reactor(s).

Cross-corrugated elements allow efficient heat transfer from the reactorwall to the gas stream. They are also suitable for use in the process ofthe invention especially in the sections with heat exchange.

Other catalysed structured elements can also be applied in the processof the invention such as high surface structured elements.

Examples of structured catalysts includes catalysed monoliths, catalysedcross-corrugated structures and catalysed rings (e.g pall-rings).

Both with catalysed hardware applied directly to the wall of the reactorand with structured catalysts, the amount of catalyst can be tailored tothe required catalytic activity for the steam reforming reactions at thegiven operating conditions. In this manner the pressure drop is lowerand the amount of catalyst is not more than needed which is especiallyan advantage if the costly noble metals are used.

In more conventional applications with pellets, the steam reformingreactors are often designed to maximise heat transfer and pellets aresimply placed in channels where the process gas flows often resulting ina vast excess of catalytic activity.

In yet another aspect of the present invention, the flow through thecatalyst may be upflow when catalyst hardware or structured catalystsare used. This can hardly be done in the case of pellets due to the riskof fluidisation. One advantage of this specific embodiment is thatsubstantial degree of piping may be avoided reducing plant cost.

Another possibility is that the tube diameter can be reduced by use ofcatalysed hardware. It is generally recognised that the ratio of thetube diameter to the diameter of catalyst pellets should be above 4-5.To avoid excess pressure drops this minimises the acceptable diameter ofthe tube (or other channel geometry). With a structured catalyst or withcatalysed hardware this constraint is eliminated opening the possibilityfor more compact reformers.

Similar advantages can be obtained if the structured catalyst is in theform of ceramic monoliths or ceramic cross-corrugated structures withactive catalyst material.

Reference is made to FIG. 2 in which a specific embodiment of theinvention is illustrated. The tail gas (2) is preheated by heater orheat exchanger (3) giving a heated tail gas stream (4).

A hydrocarbon containing feedstock (1) is treated in a number ofsequential steps comprising the following (two sequential steps areshown in FIG. 2):

-   -   Optional addition of tail gas (5) resulting in heat exchanger        feed stream (6)    -   Heating heat exchanger feed stream (6) resulting in stream (8)        and optionally adding to stream (8) an amount of tail gas (9) to        form reactor feed stream (10).    -   Passing the reactor feed stream (10) into an adiabatic steam        reforming reactor (11) in which the following reactions occur:        CH₄+H₂O        3H₂+CO  (1)        CO+H₂O        H₂+CO₂  (2)        C_(n)H_(m) +nH₂O        nCO+½(m+2n)H₂  (3)

These steps are continued until the desired temperature and exit gascomposition is obtained. The effluent (12) from the last of the reactorscan optionally be mixed with tail gas (13) to form the combined stream(16). This stream may be further heated in heater or heat exchanger (14)giving stream (17). Tail gas may optionally be added to this stream toform the ATR feed stream (18). The ATR feed stream (18) and oxidant (19)is fed to the ATR (20) in which synthesis gas is produced and withdrawnas product stream (21).

Another alternative is to use one or more adiabatic reactors in seriesas described above upstream one heated reactor (heat exchange reformer).

The hydrocarbon containing feed stream may be pre-reformed in anadiabatic pre-reformer prior to steps 1-3) above. The heat source forthe heat exchangers is one or more hot gas streams not shown in FIG. 2.An example of such a hot process stream is the effluent stream from theATR reactor.

This concept has a number of advantages in addition to those describedearlier:

-   -   Complete decoupling of the reactor design and heat exchanger (or        heater design)    -   Easier change of catalyst    -   Higher hydrogen to olefin ratio and higher steam to higher        hydrocarbon ratio at the inlet to the adiabatic reactors if the        tail gas is injected at several locations (unless all tail gas        is injected downstream the reformer unit). This means that the        risk of forming detrimental carbon on the catalyst is reduced    -   Tailoring catalysts to the different operating conditions in the        adiabatic reactors. One example is to use Nickel based catalysts        in the first reactors(s) where the temperature is lowest and use        noble metals in subsequent reactors. Often the amount of steam        needed to avoid carbon formation increases with temperature.        Since noble metals are more resistant to carbon formation than        Nickel, these should be used at the higher temperatures.

The heat source for the reformer unit may be either from a fired heateror a hot process gas from elsewhere in the plant including the effluentfrom the ATR. The former alternative may have the disadvantage thatadditional natural gas or another hydrocarbon feedstock may have to beburned to provide the necessary heat. Part of this heat may be recoveredby preheating the tail gas and/or the feed for the adiabaticpre-reformer by using the effluent from the ATR.

In case the effluent from the ATR is used as heat source, a risk ofmetal dusting corrosion exists. This can be prevented by adding a smallamount (0.02-20 ppm v/v) of sulphur or sulphur containing compounds tothe effluent from the ATR (or to the ATR feed stream). Alternatively,materials with high resistance to metal dusting can be employed in thereformer unit at least on the ATR effluent side. Examples includeInconel 693 or other materials with high resistance to metal dustingincluding coatings.

The use of highly metal dusting resistant materials may also be combinedwith addition of sulphur as described above.

EXAMPLES Example 1

Natural gas with a composition of 95% methane, 3.5% ethane, and 1.5%propane is used. In all cases the amount of natural gas feed has beenmaintained at 1000 Nm³/hr. A small flow of hydrogen of 20 Nm³/hr isadded to the natural gas in all cases. The steam to carbon (S/C) ratiois defined as the molar ratio of steam to carbon derived fromhydrocarbons in the natural gas (i.e excluding carbon in tail gas). Thetail gas used in all examples has one of the two compositions given inTable 1. Tail gas #2 is lean in carbon monoxide content.

TABLE 1 Tail Gas #1 Tail Gas #2 Concentration Concentration Compound(mole %) (mole %) Hydrogen 31.1 31.1 Carbon 27.8 4.0 Monoxide Methane3.7 3.7 Nitrogen 4.0 4.0 Carbon 30.4 53.2 Dioxide Ethane 1.5 1.5Ethylene 1.5 1.5 Propane 0.0 1.0 Propylene 0.0 1.0

Example 1A Comparative Example

In this case desulphurised natural gas is mixed with steam and tail gas#1. The resultant mixture is heated to 430° C. and fed to an adiabaticpre-reformer. The pre-reformed mixture is heated to 600° C. Theresultant mixture is fed to the Autothermal Reformer together with anoxidant (oxidant composition: 99.5% oxygen and 0.5% Argon) in which thesynthesis gas is produced. The feed temperature of the oxygen is 200° C.The amount of tail gas added is adjusted to give a hydrogen-to-carbonmonoxide ratio in the synthesis gas stream equal to 2.00. The ATReffluent temperature is 1050° C. All reactions are assumed to be inequilibrium at reactor outlet conditions. The pressure throughout thesystem is 2.48 MPa. The tail gas temperature is 200° C. Thesteam-to-carbon ratio is 0.6.

Example 1B Comparative Example

In this case a heat exchange reformer has been placed between theprereformer and the autothermal reformer. Tail gas #1 is added upstreamthe prereformer. The amount of tail gas is adjusted such that the ratioof carbon dioxide to carbon from hydrocarbons in the natural gas is 20%.This corresponds to one embodiment disclosed in U.S. Pat. No. 6,525,104.The exit temperature from the heat exchange reformer is 600° C. Thepressure, the pressure drop, the inlet temperature to the adiabaticprereformer, the oxygen temperature at the ATR inlet and the exittemperature from the Autothermal Reformer are as in example 1A. Thesteam-to-carbon ratio is 0.6 as defined in example 1A.

Example 1C Comparative Example

Example 1C is identical to 1B except that pure carbon dioxide is addedinstead of tail gas. In addition, the carbon dioxide is added downstreamthe prereformer and upstream the heat exchange reformer at a temperatureof 200° C.

Example 1D

Process of the invention with one adiabatic step.

This is similar to example 1A except that the tail gas (#1) is addeddownstream the adiabatic prereformer and after the heating of theprereformer effluent to 600° C. The tail gas temperature is 200° C.

Example 1E

Process of the invention with one adiabatic step and one endothermicstep.

This example is similar to example 1D except that a reformer unit hasbeen added downstream the adiabatic reformer. This corresponds to oneadiabatic step and one endothermic step. Tail gas #1 with a temperatureof 200° C. is added to the effluent from the reformer unit.

Example 1F

Process of the invention with one adiabatic step and one endothermicstep.

This example is identical to example 1E with the exception that 50% ofthe tail gas is added to the effluent from the reformer unit and theremaining 50% is added downstream the adiabatic reformer.

In Table 2 the production of synthesis gas (hydrogen and carbonmonoxide) for examples 1A-1F is given relative to the natural gas andoxygen consumption. The hydrogen-to-carbon monoxide ratio in thesynthesis gas is also given and tail gas #1 was used.

TABLE 2 Synthesis gas Synthesis gas Hydrogen-to- production productioncarbon mon- (Nm3 syngas (Nm3 syngas oxide ratio produced/Nm3produced/Nm3 in synthesis oxygen natural gas gas (H₂/CO, Exampleconsumed) consumed) mole/mole) 1A 5.03 3.14 2.00 1B 5.17 3.44 1.72 1C5.23 2.99 1.86 1D 5.11 3.16 2.00 1E 5.49 3.22 2.00 1F 5.39 3.21 2.00

In Table 3 below, the given inlet and outlet temperatures for examples1A, 1B, 1D, and 1E of the adiabatic prereformer are given. Thecalculated reaction quotients at chemical equilibrium for the carbonformation reaction (5) from methane is also given at the inlet andoutlet temperatures.

The equilibrium constant for reaction (5) at the inlet and outlettemperatures are also given assuming that carbon is in the form ofgraphite. It is recognised that the true equlibrium constant for carbonformation on a catalyst is different and to some extent depending uponthe catalyst. However, for comparative and illustrative purposes, theuse of the equilibrium constant for graphite is adequate.

In Table 3, the ratio of steam to moles of carbon from higherhydrocarbons (in the examples these are ethane, ethylene and propane)and the ratio of steam to ethylene in the prereformer inlet gas are alsogiven.

TABLE 3 T_(inlet) T_(exit) Q_(c), _(in) Q_(c), _(out) K_(p), _(in)K_(p), _(out) Case (° C.) (° C.) (atm · a) (atm · a) (atm · a) (atm · a)S/HHC S/C₂H₄ 1A 430 493 0.074 0.25 0.122 0.41 4.83 149 1B 430 560 0.0490.52 0.122 1.23 4.07 61 1C 430 410 0.155 0.11 0.122 0.079 5.56 Inf 1D430 410 0.155 0.11 0.122 0.079 5.56 Inf 1E 430 410 0.155 0.11 0.1220.079 5.56 Inf 1F 430 410 0.155 0.11 0.122 0.079 5.56 Inf Inf = infinite(no ethylene present in natural gas)

The definitions are as follows:

T: Inlet temperature to and exit temperature from adiabatic prereformer

Q_(c): Reaction quotient (P² _(H2)/P_(CH4)) for reaction (5) atprereformer inlet and outlet temperature (and pressure) afterestablishment of equilibrium of steam reforming and shift reactions.

K_(p): Equilibrium constant for reaction (5) at inlet and outlettemperature of prereformer.

S/HHC: Ratio of steam to carbon from higher hydrocarbons at prereformerinlet.

S/C₂H₄: Ratio of steam to ethylene at prereformer inlet.

It is seen from Tables 2 and 3 that the present invention (1D, 1E, and1F) provides considerable improvement.

Using the processes described is 1E and 1F a considerable increase inthe syngas productivity per unit of oxygen is found. In addition, thesyngas production per unit of natural gas feed consumption is improvedwith the exception of comparative example 1B. However, with 1B, it isnot possible to produce a syngas with the desired composition ofH₂/CO=2.00. In addition, in example 1B considerable recirculation isneeded requiring a large recirculation compressor.

Example 1C provides a reasonable syngas productivity per unit of oxygenconsumed. However, this concept suffers from the fact that aCO₂-separation step is needed and the synthesis gas productivity perunit of natural gas feed consumed is low.

A comparison of 1A and 1D shows a small improvement in terms ofsynthesis gas productivity by recirculating the tail gas to a positiondownstream the prereformer.

In Table 3, the advantages of the present invention are furtherillustrated. In the comparative examples 1A and 1B, the reactionquotients Q_(c) are lower than the equilibrium constants, K_(p), both atthe inlet and the outlet of the prereformer. The opposite is the case inexamples 1D, 1E and 1F of the present invention. This means that thepresent invention can be operated at a lower steam-to-carbon ratio (orwith a larger margin to carbon formation) than the comparative examples1A and 1B without risk of carbon formation in the prereformer (for agiven catalyst).

It is also noted that the ratio of steam to carbon from higherhydrocarbons in the feed stream to the prereformer is higher accordingto the concepts described in the present invention. This may also beinterpreted as reduced risk of carbon formation and/or a higher marginto the carbon formation limits for a given catalyst.

Finally, there are no olefins in the feed to the prereformer. Even verysmall amounts of olefins in the feed gas may cause rapid formation ofcarbon on a given catalyst. Hence, this is also a pronounced advantageof the present invention.

Example 2

This example is similar to example 1. In all the following sub-examplestail gas #1 is used.

Example 2A is a comparative example identical to Example 1A except thatthe prereformed mixture is heated to 700° C. Example 2D is identical toExample 1D with the exception that the prereformed mixture is heated to700° C. before mixing with tail gas. Examples 2E and 2F are identical to1E and 1F except that the exit temperature from the reforming unit is700° C. In all of these cases the H₂/CO-ratio has been adjusted to 2.00by the amount of tail gas recycled.

In Tables 4 and 5 the results for Examples 2A, 2B, 2E and 2F are given.It is observed that the advantage of the ability to operate with a lowercontent of steam in the feed gas is maintained also in this case. Thesecond advantage in terms of higher syngas productivity is also evidentirrespective of whether the tail gas is added downstream the reformingunit or split equally between upstream and downstream the reformingunit.

TABLE 4 Synthesis gas Synthesis gas production production (Nm3 syngas(Nm3 syngas produced/Nm3 produced/Nm3 oxygen natural gas Exampleconsumed) consumed) 2A 5.29 3.19 2D 5.35 3.20 2E 6.35 3.35 2F 6.31 3.34

TABLE 5 T_(inlet) T_(exit) Q_(c), _(in) Q_(c), _(out) K_(p), _(in)K_(p), _(out) Case (° C.) (° C.) (atm · a) (atm · a) (atm · a) (atm · a)S/HHC S/C₂H₄ 2A 430 496 0.073 0.26 0.122 0.43 4.80 141 2D 430 410 0.1550.11 0.122 0.079 5.56 Inf 2E 430 410 0.155 0.11 0.122 0.079 5.56 Inf 2F430 410 0.155 0.11 0.122 0.079 5.56 Inf Inf = infinite (no ethylenepresent in natural gas)

Example 3

Example 3 is identical to Example 2E except that the steam-to-carbonratio has been varied. The results are given in Table 6. Tail gas #1 isused in all cases.

The prereformed mixture is steam reformed in a heat exchange reformingreactor where the required heat is supplied by heat exchange with theeffluent stream from the ATR.

Tables 6a and 6b show the results obtained at various steam-to-carbonratios.

Definitions:

Reformer Unit Duty: Heat input (per Nm3 natural gas feed) required toreach the exit conditions from the reformer unit (T=700° C. and chemicalequlibrium of methane steam reforming and shift reactions).

Dry mole %: 100×(moles of H₂+CO in syngas)/(moles of syngas-moles ofsteam in syngas).

Recycle tail gas: Amount of tail gas recycle required to obtain thedesired ratio of H₂/CO in the ATR effluent gas (H₂/CO=2.00).

Heat Exchange Reformer effluent Temperature (° C.): Temperature of ATReffluent gas after cooling by heat exchange in heat exchange reformer.

TABLE 6a Synthesis gas Synthesis gas production production (Nm3 syngas(Nm3 syngas produced/Nm3 produced/Nm3 Heat Exchange Steam-to- oxygennatural gas Reformer Duty carbon ratio consumed) consumed) (Kcal/Nm³ NG)0.60 6.35 3.35 659 0.40 6.20 3.18 558 1.00 6.56 3.61 838

TABLE 6b Heat Exchange Reformer Recycle effluent Steam-to- Dry % H₂ + COtail-gas Temperature carbon ratio in syngas (Nm³/Nm³ NG) (° C.) 0.6094.2 0.355 616 0.40 95.0 0.222 639 1.00 92.1 0.618 595

It may appear attractive to increase the steam-to-carbon ratio strictlyfrom a syngas productivity prospective (assuming enough tail gas isavailable). However, the advantage of a smaller content of inerts in thesynthesis gas, smaller required duty (and thereby heat transmissionsurface), a smaller tail gas recycle (compressor) and generally smallerflows will usually be more important, thus favouring a smallersteam-to-carbon ratio. It can also be noted that with lowsteam-to-carbon ratio, the effluent temperature from the heat exchangereformer (heat supplying side) is highest indicating a moderately higherdriving force for the heat transfer. The best choice will depend on siteand project specific issues.

Example 4

Examples 4A, 4D, 4E, and 4F are identical to Examples 2A, 2D, 2E and 2Fexcept that tail gas #2 is used. Example 4G is similar to 4F except that75% of the tail gas is added upstream the reformer unit and 25%downstream.

With tail gas #2, which is lean in CO content, it seems at the givenconditions that a marginal advantage exists by adding at least part ofthe tail gas upstream the reforming unit (downstream the prereformer).Table 7 shows the production of synthesis gas (hydrogen+carbon monoxide)relative to the natural gas and oxygen consumption for Example 4.

From Table 8, it can be seen that the present invention offers theadvantage of ability to operate either with a larger margin to carbonformation or at lower steam-to-carbon ratio with a given catalyst. TheS/Colefin ratio is the ratio of steam to olefins (sum of ethylene andpropylene) in the feed to the adiabatic prereformer.

TABLE 7 Synthesis gas Synthesis gas production production (Nm3 syngas(Nm3 syngas produced/Nm3 produced/Nm3 oxygen natural gas Exampleconsumed ) consumed) 4A 5.22 3.16 4D 5.18 3.15 4E 6.11 3.29 4F 6.20 3.314G 6.25 3.31

TABLE 8 T_(inlet) T_(exit) Q_(c), _(in) Q_(c), _(out) K_(p), _(in)K_(p), _(out) Case (° C.) (° C.) (atm · a) (atm · a) (atm · a) (atm · a)S/HHC S/C_(olefin) 4A 430 459 0.075 0.136 0.122 0.213 4.32 93 4D 430 4100.155 0.11 0.122 0.079 5.56 Inf 4E 430 410 0.155 0.11 0.122 0.079 5.56Inf 4F 430 410 0.155 0.11 0.122 0.079 5.56 Inf 4G 430 410 0.155 0.110.122 0.079 5.56 Inf Inf = infinite (no olefins present in natural gas)

Example 5

In this example two adiabatic reactors are placed in series and upstreama heat exchange reformer. The first reactor is an adiabatic prereformerwith an inlet temperature of 430° C. One tenth (10%) of the total amountof tail gas (#1) is added downstream the adiabatic prereformer. Thecombined mixture is heated in an interstage heater to 485° C. and passedto the second adiabatic reformer. The effluent from the second adiabaticreformer is passed directly without further tail gas addition to theheat exchange reformer.

The remaining tail gas is added downstream the heat exchange reformer.The steam-to-carbon ratio (as defined in example 1) is 0.60. The heatexchange reformer exit temperature is 600° C. Other process parametersare as in Example 1. Key results are shown in Table 9.

Table 9 shows the results obtained with two adiabatic reformers inseries and upstream a heat exchange reformer as described in Example 5.Inlet and exit refer to the second adiabatic reformer.

TABLE 9 Heat Exchange Reformer Duty 265 (kcal/Nm³ NG) Interstage heaterduty 73 (Kcal/Nm³ NG) S/HHC, inlet 613 S/C₂H₄, inlet 1226 T_(exit) (°C.) 469 Q_(c), inlet 0.3544 Q_(c), outlet 0.2722 K_(p), inlet 0.3537K_(p), outlet 0.2633

It is seen from Table 9 that approximately 220 of the required duty istransferred in the interstage heater. This reduces the size of the heatexchange reformer. Hence, part of the required heat transfer surface maybe designed without considering optimisation of the reaction systemsimultaneously. The adiabatic reformer can also be optimised withoutconsidering heat exchange surface. The content of ethane and ethylene inthe feed gas to the adiabatic reformer is very low reducingsubstantially the risk of carbon formation on the catalyst as comparedto having all the tail gas injected into the adiabatic prereformer. Atthe same time the contents of higher hydrocarbons in the feed gas to theATR is reduced. This is an advantage in terms of margin to sootformation.

The Q_(c) and K_(p) values in Table 9 indicate that ideally the secondadiabatic reformer can be operated without formation of graphite. It isknown that nickel catalysts are more resistant to carbon formation frommethane than thermodynamics predict using graphite. Hence, the adiabaticprereformer and the second adiabatic reactor may be operated with nickelcatalysts, while the heat exchange reformer needs a more carbonresistant catalyst based on noble metals. In any case the amount ofnoble metal is reduced using the inventive process in this example. Theaccurate location of carbon limits depend on the specific catalyst.

Example 6

This example is based on Example 2E. An adiabatic prereformer is placedupstream and in series with a heat exchange reformer without interstageheating. All of tail gas #1 is added downstream the heat exchangereformer.

At these conditions after establishment of equilibrium of the steamreforming and shift reactions, there is no thermodynamic potential forthe formation of graphite at temperatures up to 526° C. In one type ofcatalyst loading, nickel catalyst is loaded in positions where thetemperature is below 526° C. and noble metal based catalysts in thewarmer positions in the reactor. The actual temperature at which thechange in catalyst is made for a given situation depends upon thepressure, natural gas composition, type of catalyst, reactor design etc.

Example 7

This example is based on Example 2E. An adiabatic prereformer is placedupstream and in series with a heat exchange reformer without interstageheating. All of tail gas #1 is added downstream the heat exchangereformer.

In this case the duty required in the heat exchange reformer is 659kcal/Nm³ natural gas feed. In this example the total amount of feed tothe plant is 100,000 Nm³/hr of natural gas. The other parameters are asin example 2E. The average heat flux to the heat exchange reformer is75,000 kcal/m² inner tube surface/hr. The heat exchange reformer has atubular geometry with a tube length of 10 meters.

Case 1: Inner tube diameter is 0.1 meter and catalyst particles with adiameter of 20 mm are used.

Case 2: Inner tube diameter is 0.05 meter and catalyst particles with adiameter of 10 mm are used.

Case 3: Inner tube diameter is 0.05 meter catalysed on the inner tubesurface with a catalyst layer with a thickness of 0.05 mm.

Case 4: As case 3, but with a catalyst layer thickness of 0.1 mm.

Cases 5 and 6: As cases 3 and 4, but with an inner tube diameter of 0.02meters.

Case 7: Inner tube diameter is 0.05 meter. The catalyst is a structuredcatalyst represented by a metallic cross-corrugated structure with asurface area of 900 m²/m³ reactor volume onto which a catalyst layerwith a thickness of 0.05 mm has been placed.

Case 8: As case 7, but with an inner tube diameter of 0.02 meters.

Table 10 shows the catalyst and reactor volume data for various catalysttypes in the heat exchange reformer of Example 7.

TABLE 10 Cat. TD D_(p) SCSA T RV CV Case Type (m) (mm) m²/m³ (mm) (m³)(m³) NOT DP 1 Pel 0.1 20 — — 22 8.8¹ 280 High 2 Pel 0.05 10 — — 11 5.5²560 v. hi 3 CH 0.05 — — 0.05 11 0.022 560 Low 4 CH 0.05 — — 0.10 110.044 560 Low 5 CH 0.02 — — 0.05 4.4 0.028 1400 Low/ M 6 CH 0.02 — —0.10 4.4 0.056 1400 Low/ M 7 STC 0.05 — 900 0.05 11 0.495 560 M 8 STC0.02 — 900 0.05 4.4 0.198 1400 M ¹Void is 60%. ²Void is 50%.Definitions:Pel: Pellets;TD: Inner tube diameter;D_(p): Characteristic catalyst pellet diameter;SCSA: Structured catalyst surface area per unit reactor volume;t: Catalyst layer thickness;RV: (Inner) Reactor volume;CV: Catalyst material Volume excl. void;NOT: Number of reformer tubes;DP: Pressure drop.

From Table 10 it is seen that the use of either catalysed hardwareattached to the inner surface of the tube or structured catalysts hasadvantage in terms of pressure drop and catalyst amount.

1. A steam reforming system for use in a process for the production ofsynthesis gas from a hydrocarbon feed stock comprising: optionally apre-reformer for adiabatic pre-reforming of the feed stock; at least afirst and last adiabatic catalytic steam reformer and/or a reformer forendothermic catalytic steam reforming; means for intermediate heating ofthe feed stock between the at least first and last adiabatic steamreformer; a down stream autothermal steam reformer connected in serieswith the reformer for endothermic steam reforming or with the lastadiabatic steam reformer; and means for addition of a carbon monoxidecontaining gas between the at least first and last adiabatic reformerand/or between the reformer for endothermic catalytic steam reformingand the autothermal reformer, wherein the means for addition of thecarbon monoxide containing gas is a tail gas recycle line from aFischer-Tropsch synthesis gas and/or a Fischer-Tropsch product work-upunit.